Hydrocarbon fuel additive



Jan. 16, 1968 J. H. GARY 3,363,999

HYDROCARBON FUEL ADDITIVE Filed Dec. 14, 19.64 2 Sheets-Sheet 1 Fly--2 INVENTOR. James H. Gary ATTORNEY .Ign. 16, 1968 J. H. GARY 3 3 ,99

HYDROCARBON FUEL ADDI'I'IVE Filed Dec. 14, 1964 2 Shegts-Sheet z- INVENTOR James H. Gary Lab/9 nu ATTORNEY,

United States Patent 3,363,999 HYDROCARBGN FUEL ADDITHVE James H. Gary, Wheatridge, (1010., assignor to Frontier Research (Jompany, Denver, Colo., a corporation of Colorado Filed Dec. 14, 1964, Ser. No. 418,950 Claims. (Cl. 44-55) This invention relates to additives for liquid hydrocarbon fuels and to the fuel produced thereby.

Liquid hydrocarbon fuels, whether compounded or uncompounded, tend to form a deposition of gums, varnishes and lacquers in the fuel storage tanks, the fuel lines, the combustion zones, and, most frequently, in the carburetion or fuel injector jets. Most commercial gasoline contains some type of a lead compound and these lead compounds tend to precipitate when exposed to atmospheric conditions.

One problem with liquid hydrocarbon fuels for internal combustion engines, turbines, or jet-type engines is the deposition which forms on the nozzles or jets which introduce fuel a thigh velocity into the combustion zone. These deposits reduce the size of openings and tend to clog the nozzles or jets, reducing efficiency and resulting in ultimate failure of the engine. The formation of the deposits from the fuel is probably caused by the fact that either the fuel injector or the carburetor jet is located quite close to the housing of the combustion chambers so that the fuel is subjected to a considerable temperature increase as the fuel passes from the supply line, through the fuel carburetion or injection system, and then into the com bustion chambers. Some of the unstable components of the fuel tend to polymerize or degrade under such temperatures, causing accumulation of solid or semi-solid deposits, which on the narrower parts of the jets and injectors restrict or alter fuel flow.

compounded fuels, which include combined characteristics of straight run and catalytically cracked fuels, introduce new problems due to the newer types of refining methods recently adopted by practically all oil companies. The cracked fuels, in particular, seem to be unstable and deteriorate quite readily under storage conditions. While the blending of the cracked fuels with straight run stocks alleviates the problem, it does not solve it, and deterioration exists to the detriment of the operation of the engine using the fuel.

The voluminous prior art attests to the tremendous amount of work which has been accomplished in the field of additives for hydrocarbon fuels. in general, the addilives of the prior art were intended to attack a specific problem for a particular fuel in an attempt to find a solution for that specific problem. In addition, the art seems to recognize that there is a difference in the problems encountered in various types of fuels, for example, gasoline, diesel fuel, and fuel oils, and have tended to develop additives for a particular fuel.

According to the present invention I have provided a novel composition which is highly effective when added in small amounts to hydrocarbon fuels. The additive is a mixture of at least three components which cooperate in a synergistic action on the hydrocarbon fuel to reduce deposits in the fuel system and in the combustion chambers. The additive, furthermore, modifies any existing accumulated deposits in gasoline internal combustion engines to reduce the octane requirement of the engine. The additive solubilizes gums, lacquers, varnishes and resins which may have formed in the fuel and reduces those not completely soluble to sub-microscopic particles to thereby substantially improve th efficiency of the combustion of the fuel. This increases power, reduces fuel consumption and produces fewer unburned hydrocarbons and carbon monoxide, in the exhaust. Also, additional stability is imparted to those fuels which contain lead prod-, ucts, normally gasolines. The additive in gasoline retards any compression-excited preignition, thereby reducing detonation and rumble. When used as an additive in gasolines, professional drivers report that greater acceleration results and a smoother running engine is provided. Further, the additive reduces the voltage requirement necessary to ignite fuel mixtures in spark ignited gasoline engines.

While some of the components of the mixture have been used as additives in various types of fuels for specific purposes, this particular combination produces a synergistic effect to exert beneficial effects on the fuel greater than that attained by the individual components.

Included among the objects and advantages of the invention is a hydrocarbon fuel which prevents detrimental deposits in hydrocarbon fuel systems as well as in the combustion chambers using such fuels. The additive modifies any existing accumulated deposits in gasoline engines and reduces the octane requirements for effective operation of the engines.

A further object of the invention is to provide an additive which disperses precipitated gums, lacquers, varnishes and polymers in hydrocarbon fuels, reducing them to submicroscopic particles to thereby improve the efliciency of combustion of the hydrocarbon fuels.

Another object of the invention is to provide an additive which stabilizes hydrcarbon fuels containing lead.

A still further object of the invention is to provide an additive for hydrocarbon fuels which solubilizes sludges and water present in storage tanks for more efiicient combustion of the components in the fuel and to prevent additional suldge from being precipitated in the entire system.

Yet another object of the invention is to provide an additive which retards compression-excited preignition and thereby reduces detonation and rumble in internal cornbustion engines.

These and other objects and advantages of the invention may be ascertained by referring to the following description which is intended as illustrative of the invention and not as a limitation thereof.

In the appended drawings:

FIG. 1 is an electron microscope photograph at 4800 enlargement of gasoline not treated with the additive, showing the substantial amount of precipitates in the fuel;

FIG. 2 is an electron microscope photograph at 4800 enlargement of the same gasoline at that of FIG. la treated with the additive of the invention;

FIG. 3 is an electron microscope photograph at 4800 enlargement of diesel fuel not treated with the additives; and

FIG. 4 is an electron microscope photograph at 4800' enlargement of the same diesel fuel of FIG. 2a treated with the additive of the invention.

The additive of the invention is highly effective in use with various types of hydrocarbon fuels which include gasoline (including leading gasolines), diesel fuels, fuel oils for stationary engines and furnaces, residual fuels and the like. In general, the additive is a mixture of liquid organic compounds which are soluble in hydrocarbon fuels, at least to the extent they are present, the preferred components being an organic amine, an acrylic polymer and methylal. The three ingredients are premixed to form a solution (which may include a hydrocarbon diluent) and the mixture is then admixed with fuel on the basis of a range of one part of additive to one to ten thousand parts of fuel (1:1000 to 1:10,000). By adding isopropyl alcohol to the mixture, additional benefits can be achieved, such as the preventing of freezing of water in the fuel in storage tanks and lines and the preventing of freezing of water included in the fuel and water which has condensed from the air mixed with the fuel in the carburetor system or injection system of combustion engines, and additionally helps to prevent depositions in the fuel, the fuel lines and tank of the fuel system.

The acrylic polymer which may be used in the formulation of the present additive is preferably a methacrylate resin which is hydrocarbon fuel soluble and is generally a basic amino nitrogen-containing addition type polymer of a plurality of polymerized ethylenically unsaturated compounds, one of which is amine free and contains from about 8 to 18 carbon atoms in an aliphatic hydrocarbon chain which in the polymer is not part of the main polymer chain, and one of which, as it exists in the polymer, contains a basic amino nitrogen in the side chain. A preferred composition is sold by E. I. duPont de Nemours and Company of Wilmington, Del., under the name FOA2." The product sold under that name is generally considered a methacrylate polymer prepared from n-octyl methacrylate and beta-diethylamino-ethyl methylacrylate. It may be used in the additive mixture so as to provide an amount in the fuel in a ratio of 2 to 50 parts per 1,000,000 and preferably in the range of from 4 to 9 parts per 1,000,000 parts of fuel.

The methacrylate polymer is commercially sold in solution with a hydrocarbon diluent, and the amount mixed with the other ingredients must take this into account to provide sufficient polymer within the useful range.

The organic amine which is used in the mixture is a mixture of tertiary acyclic amines, preferably a mixture of lower molecular weight aliphatic tertiary amines. One preferred mixture is sold by E. I. duPont de Nemours and the trade name FOA3. The organic amine may be used to provide a quantity in the fuel of from 5 to 100 parts per 1,000,000 parts of fuel, and preferably in the range of 8 to 20 parts of the amine in 1,000,000 parts of fuel.

The methylal may be used in concentration of 25 to 1,000 parts per 1,000,000 parts of fuel, and preferably in the range of 40 to 100 parts of the methyla-l to 1,000,000 parts of fuel. Isopropyl alcohol may be added to the mixture as a deicer and it is used in the amount of to 300 parts per 1,000,000 parts of fuel, but preferably in the range of 18 to 50 parts per 1,000,000 parts of fuel.

Of substantial importance is the fact that the additive may be used for gasoline, diesel fuels, jet and turbine fuels, burner fuels and the like. In a preferred formulation, the same formulation may be used for any of the fuels and still provide the improved results for the fuel.

The preparation of an additive embodying the invention is illustrated in the following examples. It will be understood that different ranges of the individual components may be used as above defined, and that each particular formulation is highly effective for gasoline and diesel fuels, burner fuels, jet fuels, aircraft turbine fuels and the like. The formulation has substantial value as an additive when used on a basis of 1 part of additive to 1,000 parts of fuel. However, it may be effectively used in various blendings, for example 1 to 8000; 1 to 5000; 1 to 4000; 1 to 2000; 1 to 1000.

Example The following components is in the amounts indicated were mixed together to form an additive which was to be added to a hydrocarbon fuel in the stated ratio of 1 part of the mixture to the indicated number of parts of fuel:

l 50% polymer and 50% diluent.

When added to gasoline on the basis of 1 part of the additive mixture to the stated parts of gasoline, whether regular or premium, there is achieved increased combustion of the gasoline in a gasoline engine. The additive produces a smoother running engine with more power. In actual highway operation using additive B, vehicles which had been operating on untreated gasoline, when operating with gasoline treated with additive B, achieved in excess of 5% more mileage per unit of fuel. Thus, the additive gives fuel economy. Using the gasoline with the additive, there are reduced unburned hydrocarbons in the exhaust, and the-re is an actual reduction of surface ignition in the combustion chambers which results in reduced ping and rumble in the engine. The carburetor of the engine is actually cleaner and there is a reduction of carbon buildup in the combustion chamber. This reduces maintenance costs of the engine and also extends engine life. Actual observation of a stationary engine (the operation is detailed below) shows that the efficiency of combustion is increased.

In the drawings attached, FIG. 1a is a microphotograph from an electron microscope of the residue in gasoline not treated with the additive shown as an enlargement of 4800 times. The dark spots in the microphotograph are actual insoluble agglomerates of unstable components in the gasoline treated with the additive on the basis of 1 to 5000, showing that the depositions in the gasoline have been solubilized and dissolved in the gasoline, leaving only minor amounts of the deposits in the gasoline and these of greatly reduced size. These microphotographs demonstate the deposits when treated become actually a part of the solution, thereby showing the effectiveness of the additive.

The microphotograph of FIG. 2a shows an untreated diesel fuel at a 4800 enlargement, taken from an electron microscope. FIG. 2b shows the same fuel treated with applicants additive on the basis of 1 to 5000, and again the microphotograph is on the basis of 4800 times. This shows that the deposits are solubilized. In each of the microphotographs of the figures, the solution is a typical sample and when thoroughly mixed, the entire solution contains the sediment and deposits suspended throughout the fuel.

In addition to the advantages given above, fuel treated with the additive of the invention does not contribute to normal fuel corrosion effects on metals. Tests conducted on a series of samples containing from 1: 1000 to 1:10,000 parts of additive to fuel showed no increase in corrosive effects. These corrosion tests were performed according to the procedure outlined in ASTM Standard D-56, Copper Corrosion by Petroleum Products (Copper Strip Test).

Additionally, there is a substantial increase in the storage stability as shown by a test, referred to herein as the induction period, which was conducted according to the procedure outlined in ASTM Standard D525-55, Oxidation Stability of Gasoline (Induction Period Method). The longer the induction period in minutes, the better the storage stability, as this is an accelerated test. The additive of the invention is effective for long-term storage since the fuel containing it has substantially improved stability. This includes leaded gasolines, i.e., those containing lead alkyl compounds, which are quite unstable.

The following table summarizes the corrosion and oxidation stability testing:

TABLE 2.REGULAR GASOLINE Corrosion at 122 F.

Induction Period, Minutes Additive Blending Ratio Neg. Neg. Neg. Neg. Neg. Neg.

No additive Further, laboratory tests reveal that the additive does not raise or lower the octane ratings of gasolines and does not appreciate or depreciate the cetane rating of diesel fuels. Tests were conducted using a Sun Model 510 test stand with oscilloscope and combustion analyzer. This test showed that the additive reduces the voltage requirement necessary to ignite fuel mixtures in spark ignited gasoline engines. These tests further prove extended spark plug life, quicker starting and increased combustion efficiency. In compression-ignited diesel engines, use of the additive substantially reduced exhaust smoke emission.

In an independent laboratory test of premium gasoline on a stationary engine, a used 371 cubic inch Oldsmobile V-8 engine with substantial combustion chamber deposits was utilized. No internal cleaning was performed during or prior to the test. Each engine test was evaluated on a dynamometer stand at full throttle and constant speed condition. Each test was conducted for one hour periods after a purge run. The tests were conducted with the engine air cleaner removed and the engine power output was observed by an electric eddy current dynamometer with a 300 horsepower absorption capacity. The engine fuel consumption was measured on a weight basis of fuel consumed. The following table summarizes the data from operation of the engines:

TABLE 3 Std. Speed Fuel, nd. BSFC Fuel Code r.p.m. lbs/hr. Corr. BE]? 1 lbs./bhp-hr.

Factor GA338 2, 402 79. 5 1. 056 152. 1 0. 523 (IA-342 2, 403 77. 5 1. 093 156. 6 0. 495

1 BHP=Brake Horse Power. 2 BSFC=Brack Specific Fuel Consumption.

No'rE.-GA338=Froutier Premium Untreated. GA-342=Frontier Premium plus Additive. Ihe difference in the BET is a gain of 3.0% and the difference in the BSFC is a gain 01' 5.7%.

Since the additive is used in small amounts, the cost of treatment per gallon is very nominal and, in fact, the increased performance reduces the actual cost of fuel for operation. For example, the increase in mileage more than compensates for the slight additional cost of the additive, and, of course, the reduced maintenance costs also reduce overall expense of engine operation.

This additive revealed excellent benefits in use with burner and residual fuels in boiler heating operations. In tests conducted in a large boiler installation, injector cups which normally are cleaned daily, needed cleaning only every seventh day. Sludge accumulations in fuel storage tanks were 85% solubulized within 30 days after original treatment with the additive and subsequent continued treatment of fuel additions. Soot deposits on boiler tubes and flues were reduced 50%. Increased combustion of the fuel allowed fuel flow to be retarded with no reduction of boiler temperatures and pressure.

While many variations of the invention will occur to those skilled in the art, it is understood that dilferent embodiments of the invention are intended to be within the spirit and scope of the invention, except as defined in the appended claims.

I claim:

1. An additive for hydrocarbon fuels which reduces deposits in and improves stability of such fuels, and increases power of and reduces fuel consumption in engines using such fuels, comprising an intimate mixture of the following ingredients each in an amount to be present in a hydrocarbon fuel in the started range of parts per million parts of fuel:

said organic amine being a mixture of acyclic tertiary amines having from 1 to 18 carbon atoms in each cham substituent on the nitrogen carbon of the amine and being hydrocarbon fuel soluble at least to the extent in which it is present; said acrylic polymer being a fuel soluble basic amine nitrogen containing addition type polymer of a plurality of polymerizable ethylinically unsaturated compounds, at least one of which compound is amine free and contains from 8 to about 18 carbon atoms and aliphatic chain which in the polymers is not part of the main chain, and said mixture being dissolved in a hydrocarbon diluent.

2. An additive according to claim 1 which includes isopropyl alcohol in an amount to be present in such a hydrocarbon fuel in an amount of from. 15 to 300 parts per million parts of fuel.

3. An additive for hydrocarbon fuels which reduces deposits in and improves stability of such fuels, and increases power of and reduces fuel consumption in engines using such fuels, comprising an intimate mixture of the following ingredients each in an amount to be present in a hydrocarbon fuel in the stated range of parts per million parts of fuel:

Organic amine 8-20 Methylal 40-100 Acrylic polymer 4-9 said organic amine being a mixture of acyclic tertiary amines having from 1 to 18 carbon atoms in each chain substituent on the nitrogen carbon of the amine and being hydrocarbon fuel soluble at least to the extent in which it is present; said acrylic polymer being a fuel soluble basic amine nitrogen containing addition type polymer of a plurality of polymerizable ethylinically unsaturated compounds, at least one of which compound is amine free and contains from 8 to about 18 carbon atoms and an aliphatic chain which in the polymers is not part of the main chain, and said mixture being dissolved in a hydrocarbon diluent.

4. A hydrocarbon fuel comprising a major part of a hydrocarbon fuel and the following each in an amount in the stated range on the basis of parts per million parts said organic amine being a mixture of acyclic tertiary amines having from 1 to 18 carbon atoms in each chain substituent on the nitrogen carbon of the amine and being hydrocarbon fuel soluble at least to the extent in which it is present; said acrylic polymer being a fuel soluble basic amine nitrogen containing addition type polymer of a plurality of polymerizable ethylinically unsaturated compounds, at least one of which compound is amine free and contains from 8 to about 18 carbon atoms and an aliphatic chain which in the polymers is not part of the main chain, and said mixture being dissolved in a hydrocarbon diluent.

5. A hydrocarbon fuel according to claim 4 wherein isopropyl alcohol is present in the fuel in an amount in the range of from 15 to 300 parts per mill-ion parts of fuel.

References Cited UNITED STATES PATENTS 1,582,420 4/ 1926 Nikaido 4-4-77 2,883,276 4/1959 Larsen 4455 2,974,025 3/ 196 1 Ertelt et al. 44-62 3,186,810 6/ 1965 Dunworth 44-62 FOREIGN PATENTS 714,213 8/1954 Great Britain.

DANIEL E. WYMAN, Primary Examiner.

C. F. DEES, Assistant Examiner. 

1. AN ADDITIVE FOR HYDROCARBON FUELS WHICH REDUCES DEPOSITS IN AND IMPROVES STABILITY OF SUCH FUELS, AND INCREASES POWER OF AND REDUCES FUEL CONSOMPTION IN ENGINES USING SUCH FUELS, COMPRISING AN ITIMATE MIXTURE OF THE FOLLOWING INGREDIENTS EACH IN AN AMOUNT TO BE PRESENT IN A HYDROCARBON FUEL IN THE STARTED RANGE OF PARTS PER MILLION PARTS OF FUEL:
 2. AN ADDITIVE ACCORDING TO CLAIM 1 WHICH INCLUDES ISOPROPYL ALCOHOL IN AN AMOUNT TO BE PRESENT IN SUCH A HYDROCARBON FUEL IN AN AMOUNT OF FROM 15 TO 300 PARTS PER MILLION PARTS OF FUEL. 